Disazo compounds and material colored therewith



Patented Sept. 24, 1940 UNITED STATES PATENT OFFICE DISAZO COIWPOUNDS AND MATERIAL COLORED THEREWITH No Drawing. Application May 9, 1939,

Serial No. 272,681

7 Claims.-

This invention relates to the preparation of a new series of polyazo dyestuffs. More particularly it relates to disazo dyes containing phosphorus.

I have discovered that a valuable series of water-soluble disazo dyes suitable for the coloration of organic derivatives of cellulose, silk and wool can be prepared by coupling various coupling components with the diazonium derivatives of the following general type of aromatic amines con taining the phosphonic acid group.

wherein. R represents an aromatic nucleus, R1 represents hydrogen, alkyl, alkylene, aryl, cycloalkyl, or heterocyclic groups, X represents hydrogen or an acyl group, each A represents hydrogen or a monovalent substituent and Z1 and. Z2 represent hydrogen, an ammonium radical, or an alkali forming metal. When R1 is alkyl, it includes the unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, as well as substituted alkyl groups such as hydroxyethyl, dihydroxypropyl, methoxyethyl, ethoxyethyl, sulfoethyl, sulfatoethyl; when R1 is aryl it includes phenyl, tolyl, xylyl, cresyl, nitro phenyl, chlorophenyl, sulfophenyl, and the like groups; when R1 is alkylene it includes ethylene, propylene, butylene, and amylene groups; when R1 is cycloalkyl it includes cyclohexyl, and tetrahydronaphthalene; and when R1 is heterocyclic it I includes tetrahydrofurfuryl and pyrazolone.

whereinR, R1, x, A, A, A, Z1, and Zz-have the by chemical reduction with zinc and hydrochloric meanings above given, and R2 represents aromatic, hydroaromatic and heterocyclic nuclei, and also their derivatives containing the group-CO COCHzCO-CH2R3 wherein R3 represents hydrogen, alkyl, alkylene, cycloalkyl, and aryl *5' groups, as nuclear substituents.

It is an object, therefore, of my invention to preparethe dyes of the class above described and to color cellulose organic derivatives, silk and wool in the form of threads, yarns, filaments, and 0 fabric materials therewith. Another object is to use the dyes of my invention for coloring resinous materials, lacquers, mineral and vegetable oils.

Briefly, theamino azo compounds used in the invention as the diazo components are prepared by coupling various aromatic diazonium salts with couplers containing a phosphonium group:

wherein R1, X, A, A; A and Z1 and Z2 have the same meanings as those given in the preceding formulae. The coupling components are prepared by the following general procedure:

An aromatic hydrocarbon, containing one or more monovalent substituents or not such as benzene, toluene, o-xylene, anisol, chlorobenzene, and the: like, is converted to the corresponding aldehyde by reaction with carbon monoxide in the presence of a catalyst. The resulting aldehyde is nitrated to the meta-nitro-aldehyde, and the latter then treated with phosphorus trichloride in an acetic acid solution following in general a method similar to that described by J. B. Conant and A. D. MacDonald, in the Journal of the American Chemical Society 42 2337 (1920). The ,phosphonic acid derivative thus obtained is then reduced to the corresponding amine, either acid, or by catalytic reduction with nickel and. hydrogen. For a more detailed description refer- 50 ence should be made to my copending U. S. Application Serial No. 268,822, filed April 19, 1939. The following examples serve to illustrate the preparation of the disazo compounds of my in vention. 5

Example 1 One mole of 1'-chloro-4-amino-2-hydroxy methyl phosphonic acidazo benzene is dissolved in water containing hydrochloric acid, and diazotized with 6.9 grams of sodium nitrite in the usual manner. When diozotization is complete, the diazo solution is added to an aqueous sodium carbonate solution of grams of 5,5-dimethylcyclohexandione-l,3. After the coupling reaction is complete, the mixture is made acid to litums with acetic acid and the sodium salt of the dye is salted out, filtered, and dried. The dye thus prepared colors cellulose acetate, silk and wool yellow from an aqueous solution of the dye which may contain salt. The diazo dye compound has the structural formula:

In place of 5,5-dimethyl-1,3-cyclohexandione, there may be substituted 5,5-diethyl-l,3-cyclohexandione, 5,5-dibutyl-1,3-cyclohexandione, 5- phenyl sulfonic acid-1,3-cyclohexandione, 3,5- furyl-1,3-cyclohexandione, l-phenyl sulfonic acid- 3-methyl-5-pyrozolone, 3-methyl 5-pyrazolone, barbituric acid, thiobarbituric acid, indole, 0xindole, and couplers of the type:

One mole of 1'-chloro-4-amino-5-methoxy-2- hydroxy methyl phosphonic acid-azobenzene is diazotized and added slowly to a dilute hydrochloric acid solution of cresidine. The coupling is completed by adding an aqueous solution of a basic salt such as sodium acetate, sodium carbonate, and the like. The dye is then salted out, filtered and dried. It colors cellulose acetate, silk and wool orange shades from an aqueous solution of the dye which may contain salt. The diazo dye thus produced has the structural formula:

In place of cresidine, there may be used mtoluidine, m-anisidine, 2,5-dialkoxy aniline, 2,5- dialkyl aniline, 2-alkoxy-5-haloaniline, mphenylene diamine producing red shades, mamino phenol, and a-naphthylamine.

Diazo dyes 'of the above kind containing a free amino group are capable of being further diazotized and recoupled with another coupling component, either in solution or on the fiber to be colored.

Example 3 One mole of 4'-nitro-4-amino-2-methyl acetoxy methyl phosphonic acid-azobenzene is diazotized and coupled with one equivalent of butyl-mtoluidine following the procedures of Examples 1 and 2. The dye colors cellulose acetate silk and wool red from aqueous solutions of the dye which may contain salt. The disazo dye compound thus produced has the structural formula:

One mole of the following p-amino-polyazo compound:

I 1 Cl CH3 /H 0 ONa HO-C is diazotized and coupled with one mole of dimethyl aniline in the manner described in Example 2. The dye colors cellulose acetate, silk and wool red from an aqueous solution of the dye which may contain salt. In place of dimethyl aniline there may be used methyl butyl aniline, ethyl lauryl-m-toluidine, butyl-hydroxye'thyl cresidine, benzyl glyceryl-m-chloroaniline, and coupling components of the following struc- Example 5 One mole of the following p-amino azo compound:

is diazotized and coupled with one mole of l-amino-B-naphthol following the procedure of Example 2. Cellulose acetate, silk and. wool are colored reddish-blue shades from aqueous solutions of the dye. The disazo compound thus obtained has the formula:

CxaHsa C) ONa oNa In place of 1-amino-8-naphthol there'may be substituted l-amino-5-naphthol, 1-amino-6,8-dichloro 5 naphthol, 1- ,3 -hydroxethylamclno-5- naphthol, and ethyl sodium sulfoethyl-u naphthylamine.

CHaO

HO-C

Example 6 One mole of the following p-diamino azo compound:

naphthol sulfonic acids, naphthylamine sulfonic acids, Z-hydroxy-S-naphthoic acid and its amides and esters, and 2-hydroxyanthracene-3-carboxylic acid.

Example 7 One mole of the following p-amino azo compound:

is diazotized and coupled with one mole of any of the coupling components mentioned in the preceding examples following the procedure of Examples 1 and 2.

The azo dyes of my invention being watersoluble they may be used for the direct coloration of organic derivatives of cellulose, silk and wool in the form of threads, yarns, filaments and fabric materials without the necessity of employing a dispersing 0r solubilizing agent. The dyeing operations will be conducted in accordance with the usual dyeing practice, salt being added if desired to facilitate exhaustion of the dye bath. For a more detailed description as to how the water-soluble azo dyes of my invention may be employed for the coloration of textile materials, reference may be had to U.-S. Patent No. 2,107,898 issued February 8, 1938.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters. and cellulose mixed organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate, cellulose butyrate, cellulose .acetate-propionate, cellulose ace-, tate-butyrate,. and cellulose ethers such as methyl cellulose, ethyl cellulose, and benzyl cellulose. r '1 I claim:

1. The azo compounds having the general formula:

wherein R representsa member selected nulu the group consisting of an aryl group of the benzene series, and a 'benzothiazole nucleus, R1 represents a member selected from the group consisting of hydrogen, an alkyl group, an alkylene group, a cycloalkly group, an aryl group of the benzene series, an aralkyl group, a pyrazolone group, and'a furyl group, R2 represents an aromatic group, a hydroaromatic group, anda heterocyclic group, X represents hydrogen or an acetyl group, each A represents a member select- 7 ed from the group consisting of hydrogen, an alkyl group, and an alkoxy group, and Z1 and Z2 represent hydrogen, an ammonium radical, or an alkali forming metal.

2. The azo compounds having the general formula:

A A x RN=NON=NR:

\A /H xo-o 0Z1 i\ 0 OZ:

wherein R represents a member selected from the group consisting of an aryl group of the benzene series, and a benzothiazole nucleus R2 represents an aromatic group, a hydro aromatic group, and a. heterocyclic group, X represents hydrogen or an acetyl group, each A represents a member selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group, and Z1 and Z2 represent hydrogen, an ammonium radical, or an alkali forming metal.

3. The azo compounds having the general formula:

wherein R represents a member selected from the group consisting of an aryl nucleus of the benzene series, and a benzothiazole nucleus, R2 represents an aromatic group, a hydro aromatic group, and a heterocyclic group, X represents hydrogen or an acetyl group, each A represents a member selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group, and Z1 and Z2 represent hydrogen, an ammonium radical, or an alkali forming metal.

4. The azo compounds having the general formula:

A Ar wherein R represents a member selected from the group consisting of an aryl nucleus of the benzene series, and a benzothiazole nucleus, R2 represents an aromatic group, a hydroaromatic group, and a heterocyclic group, each A represents a member selected from the group consisting of hydrogen, and an alkyl group, and an alkoxy group, and Z1 and Z2 represent hydrogen, an ammonium radical or an alkali forming metal.

6. Material made of or containing organic derivatives of cellulose colored with a dye selected from the class of azo compounds having the general formula:

wherein R represents a member selected from the group consisting of an aryl nucleus of the benzene series, and a benzothiazole nucleus, R1 represents a member selected from the group consisting of hydrogen, an alkyl group, an alkylene group, a cyoloalkyl group, an aryl group of the benzene series, an aralkyl group, a pyrazolone group and. a furyl group, R2 represents an aromatic group, a hydro aromatic group, and a heterocylic group, X represents hydrogen or an acetyl group, each A represents a member selected from the group consisting of hydrogen, an

alkyl group, and an alkoxy group, and Z1 and Z2 wherein R represents a member selected from the group consisting of an aryl nucleus of the benzene series, and a benzothiazole nucleus, R1 represents a member selected from the group consisting of hydrogen, an alkyl group, an alkylene group, a cycloalkyl group, an aryl group of the benzene series, an aralkyl group, a pyrazolone group, and a furyl group, R2 represents an aromatic group, a hydro aromatic group, and a heterocyclic group, X represents hydrogen or an acetyl group, each A represents a member selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group, and Z1 and Z2 represent hydrogen, an ammonium radical, or an alkali forming metal.

JOSEPH B. DICKEY.

CERTIFICATE OF CORRECTION. Patent No. 2,21 657. 1 September at, 191m.

JOSEPH B. DIcKEY. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction asfollows; Page 1, first column, line 1+2, after the Word "compound" insert --and--; and second column, line 5, strike out "C0-"; and that the said Letters Patent should be of the case in the Patent Office.

Signed and sealed this 11th day of February, A. D. 19in.

Henry Van Arsdal'e, (Seal) Acting Commissioner" of Patents. 

